초록
TTF (tetrathiafulvalene) 유도체의 전구체로서 5,6-dimethyl-1,3-dithiolo[4,5-b][1,4]dithiin-2-thione (화합물 3)을 로손반응에 의하여 합성하였다. 치환기의 종류에 따라 1,4-dithiin이나 티오펜이 포함된 두 가지의 서로 다른 생성물이 얻어졌고, 이들은 $^{13}C$ NMR과 고 분해능 전자충돌(HREI) 질량분석 분광학으로 특성화하였다. 화합물 3의 합성은 X-선 구조분석으로도 확인되었다. 결정학적 자료: 삼사정계, 공간군 P1, a=4.145(2)${\AA}$, b=10.600(2)${\AA}$, c=12.279(2)${\AA}$, ${\alpha}=71.440(10)^{\circ},\;{\beta}=84.30(2)^{\circ},\;{\gamma}=87.31(2)^{\circ}$, Z=2, $R(wR_2$)=0.0559(0.1416). 두 가지 생성물의 생성 기구를 비교하여 설명하였다.
As a precursor of tetrathiafulvalene (TTF) derivative, 5,6-dimethyl-1,3-dithiolo[4,5-b][1,4]dithiin-2-thione (compound 3) was synthesized by the unusual Lawesson's reaction. Depending upon the substituents such as dimethyl and diphenyl groups, two different products containing 1,4-dithiin and thiophene moieties, respectively, were obtained and characterized by $^{13}C$ NMR and high-resolution electron impact (HREI) mass spectroscopy. The formation of 3 was further characterized by X-ray structure analysis. Crystallographic data for 3: triclinic, space group P1, a=4.145(2)$\AA$, b=10.600(2)$\AA$, c=12.279(2)$\AA$, $\alpha$=71.440(10)$^{\circ}$, $\beta$=84.30(2)$^{\circ}$, $\gamma$=87.31(2)$^{\circ}$, Z=2 and R(wR$_2$)=0.0559(0.1416). The formation mechanism of two products was suggested and compared each other.